Sensing water vapour

ABSTRACT

A water vapour sensor comprises a substrate and a film of carbon nanotubes impregnated with surfactant on the substrate. The substrate is of material which is inert relative to the film. Two or mote electrical conductors are in contact with in spaced apart zones of the film, whereby the impedance of the film may be measured. The sensor is housed in housing which protects the sensor but also allows exposure of the film to water vapour.

FIELD

The present invention relates to water vapour sensor and a method ofmaking such a sensor. An embodiment of the invention relates to ahumidity sensor. Another embodiment relates to a dew point-sensor.

BACKGROUND

Water vapour sensors, in particular humidity sensors, also known ashygrometers, are well known. Hygrometers are used for many purposes:meteorology; monitoring environments within buildings; controlling airconditioning; in industry; making paper; horticulture; monitoringfoodstuffs in supply chain(r); and many other uses.

Humidity is difficult to measure. Many techniques for measuring humidityare based on relatively large physical sensors. Small electronic sensorsare used but such sensors are based on semiconductor techniques: andrequire semiconductor production facilities. For example it is known tocombine carbon nanotubes with field effect transistors for sensinghumidity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a water vapour sensor in accordancewith the invention;

FIG. 2 is a block diagram of an illustrative method of making the watervapour sensor of FIG. 1;

FIG. 3 is a plan view of a part of the water vapour sensor of FIG. 1,

FIG. 4 is a graph showing the response to humidity change of the sensorof FIG. 1 compared to a different form of sensor;

FIG. 5 is a graph showing the change of resistance to a step change inhumidity of the sensor of FIG. 1;

FIG. 6 is a graph comparing the response of the sensor of FIG. 1compared to a Testo 174H sensor;

FIG. 7 is a schematic diagram of a temperature compensated humiditysensor in accordance with the invention;

FIG. 8 is a schematic diagram of a dew point sensor including a watervapour sensor in accordance with the invention;

FIG. 9 a graph showing the change of resistance over time with changesin temperature of the sensor of FIG. 8 together with dew pointtemperature;

FIG. 10 is a graph comparing the change of resistance of the sensor ofFIG. 8 compared to a different form of sensor;

FIG. 11 is a diagram explaining the derivation of dew point using thesensor of FIG. 8;

FIG. 12 is a graph comparing results derived from the sensor of FIG. 8with results from a Testo 610 meter; and

FIG. 13 is a schematic diagram of an alternative humidity sensor inaccordance with the invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE INVENTION

Referring to FIG. 1, the water vapour sensor comprises a substrate 2 onwhich is a film 4 of carbon nanotubes impregnated with surfactant.Electrical conductors 6 and 8 are connected to spaced apart zones 60, 80(shown in FIG. 3) of the film. Surfactant maybe removed from the zones.The sensor is in a housing 10, which protects the film, substrate andconductors but which allows water vapour (e.g. humid air) to enter thehousing. The housing mechanically protects the film from damage whichmay change its resistance. The housing may for example have holes in awall 12 above the film. A sheet (not shown) porous to humid air maycover the holes inside the housing. An example of a suitable sheet is athin film with micro perforations. The housing may be of plastics or anyother suitable material which mechanically protects the film, and doesnot absorb water vapour. Plastics may be chosen because they are alsoelectrically insulative.

A measuring device 14 may be connected to the conductors 6, 8 to measurethe resistance of the film. The measured resistance is a measure of theamount of water vapour.

The carbon nanotubes may be single walled tubes or multiwalled tubes ora mixture of single and multiwalled tubes. The carbon nanotubes are amixture of metallic and semiconductive tubes.

The surfactant may be sodium dodecyl sulphate (SDS) or any othersuitable surfanctant. Other suitable surfactants include SDBS (sodiumdodecyl benzene sulfonate), CTAB (Hexadecyl Trimethyl Ammonium Bromide),and polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether, whichmay be sold as Triton X-100 (Trade Mark).

The substrate may be of plastics, ceramic, glass, silicon, paper forexample photo-paper, or my other suitable material which is inert to thefilm. The substrate may be rigid or flexible. The substrate may betransparent. A suitable substrate is PET (Polyethylene terephthalate),which is flexible and transparent.

The measuring device is an ohmmeter: such devices are well known.

One example of the water vapour sensor comprises a film 4 of singlewalled carbon nanotabes impregnated with SDS deposited on a flexiblesheet 2 of transparent PET. The carbon nanotube film of this example ofthe sensor is also transparent. The film may be about 100 nm thick. Theconductors 6 and 8 make contact with silver paste deposited on thespaced apart zones 60, 80 of the film. In this example all surfactant isremoved from the zones, but is not removed outside the zones.

Referring to FIG. 2, a method of making the sensor comprises depositingcarbon nanotubes impregnated with, and wet with, surfactant on an inertsubstrate, drying the impregnated tubes to form a film of impregnatedtubes on the substrate, and connecting spaced apart zones of the film toelectrical conductors. An example of the method comprises the followingsteps.

The process starts with single walled carbon nanotubes in dry powderform. The carbon nanotubes are put 20 in a solution of SDS in deionized(DI) water containing a concentration of SDS above the critical micelleconcentration: for example a dispersion of 0.1% wt SWNT and 1% SDS in DIwater. The mixture of carbon nanotubes and SDS is sonicated 21 toproduce an exfoliated dispersion 22 which is centrifuged 23 to produce asupernatant 24 and a remainder. The supernatant and SDS associated withthe supernatant is separated 25 from the remainder. The supernatant andSDS is then deposited 26 as a film on a substrate, in this example asheet of PET, by fluid jet printing, spray deposition or dip coating.Other deposition techniques may be used. The deposited film is thendried 27.

Surfactant is not removed: instead it is incorporated in the watervapour sensor. The presence of surfactant has been found to greatlyincrease the sensitivity of the water vapour sensor as compared to asimilar sensor but in which all surfactant has been removed.

In one example, the carbon nanotubes are sprayed onto a PET film placedon a hot plate. Temperatures up to the glass transition point of PET canbe used. In one example, the plate is held at 70° C. The deposited filmhas a thickness of for example 100 nm. In step 28, SDS is removed fromthe spaced apart zones 60, 80 (see FIG. 3) of the film and conductivecontacts applied to the zones. The SDS may be removed from the zones byapplying a mask to the carbon nanotube film to protect the film outsidethe zones and applying DI water to the zones. SDS may be removed fromthe zones by using a fluid jet printer to apply DI water to the zones.

FIG. 3 is a plan view of a carbon nanotube film 4 having spaced apartzones 60, 80 from which surfactant has been removed and conductivecontacts applied, the contacts overlapping the edge of the film onto thesubstrate 2. The conductive contacts may be silver paste or any othersuitable conductor compatible with carbon nanotubes and the substrate.

The resistance of the film may be measured using the known four pointmeasurement which eliminates contributions from contact resistance: seefor example http://en.wikipedia.org/wiki/Four terminal sensing. In thecase of four point measurement it is not strictly necessary to removethe SDS from the area of the electrical contact points on the carbonnanotube film.

The method of FIG. 2 provides a straightforward method of making ahumidity sensor in which a carbon nanotobe film is provided by simpledeposition techniques.

By not removing SDS, the carbon nanotubes deposited in the substrate areimpregnated with the SDS. As shown in FIGS. 4 and 5, it has been foundthat the SDS increases the sensitivity A of the resistance of the carbonnanotubes to water vapour (humidity) compared to a sensor B in which theSDS is removed.

The graph of FIG. 4 compares changes in the resistance A of SWNT films(measured with a Keithley 2400 Source Meter) exposed to varying relativehumidity levels when the films remain impregnated with SDS surfactantwith the resistance B when the SDS is removed. The graph shows thechange in film resistivity when repeatedly switching relative humidityfrom about 30% (lab level) to about 75% at constant temperature.Although the shapes of the curves are complex, the increased sensitivitywith the SDS impregnated film (line A) is clear.

The graph of FIG. 5 shows the change in film resistance in response to asingle step change in relative humidity from about 30% (label level) toabout 75%. Both curves A and B show very long response times, but againthe higher sensitivity of the SDS impregnated film (line A) compared tothe resistance (B) of film having no SDS is clear.

The graph of FIG. 6 charts the changes of resistance of an SDSimpregnated SWNT film in response to natural changes in lab relativehumidity over several days (blue curve). The reference relative humiditymeasurement was made with a Testo174H data logger (red curve). Over thecourse of this test the lab temperature remained, constant at 18.5° C.

Whilst the water vapour sensor of FIG. 1 provides a measure of watervapour, its resistance is also dependent on temperature The sensor ofFIG. 1 does not measure relative humidity. The sensor of FIG. 1 mayinclude a temperature sensor for use in compensating for variation ofresistance with temperature without measuring relative humidity.

A humidity sensor which measures relative humidity requires a measure oftemperature because the saturation pressure of water vapour in airdepends on temperature.

Referring to FIG. 7, a humidity sensor comprises a water vapour sensor2, 4, 6, 8, 10 as described above in combination with a temperaturesensor 40 arranged to sense the temperature of the humidity sensor. Aprocessor 42 determines a measure of relative humidity which may also becompensated for the variation of resistance of the carbon nanotube filmwith temperature. To compensate for temperature variation, the variationof resistance of a film 4 may be measured, as temperature changes buthumidity is held constant to determine the equation representingresistance variation with temperature. That equation is used tocompensate for the variation of resistance with temperature.

The temperature sensor 40 may be any suitable temperature sensorarranged to sense the temperature of the humidity sensor. In one examplethe temperature sensor is a platinum based resistor deposited on thesubstrate 2 immediately adjacent to the film, 4.

In another example the temperature sensor comprises a film of carbonnanotubes impregnated with surfactant (the same as the water vapoursensor) but encapsulated so that the film is unaffected by water vapour.The temperature sensor is in close contact with the water vapour sensorto detect its temperature.

The determination of relative humidity from a measure of temperature andhumidity is known in the art and will not be discussed here.

Referring to FIG. 8, the water vapour sensor described hereinabove maybe used in a dew point sensor. The dew point sensor of FIG. 8 comprisesa cooler, in this example a Peltier cooler 50. The cooler has a cooledface 52, which may be a ceramic substrate. A film 4 of carbon nanotubesimpregnated with surfactant, e.g. SDS, may be deposited directly on thecooled face or a sheet of PET carrying the film as described above maybe fixed to the cooled face 52. Placing the film directly on the cooledface avoids having any thermal barrier between the film and the cooledface.

A temperature sensor 54 is provided to sense the temperature of thecooled face 52 and the water vapour sensor. In this example thetemperature sensor is in contact with, or embedded in, the cooled face52.

The water vapour sensor and cooler are housed in a housing 101 having aporous face 121 which allows humid air into the housing.

A processor 56 may be provided to determine the dew point D using thesensed temperature T and the humidity measure H provided by the watervapour sensor.

Two ways of determining dew point are described below.

In one way, which does not require the processor 56, as shown in FIG. 8,the dew point sensor comprises a controller 58 which is responsive to(i) a reference value R_(D) representing a predetermined resistancevalue (which is the resistance of the film 4 when dew just forms on it)and (ii) the actual measured the resistance R_(A) of the film, which iskept equal to R_(D) to maintain the cooled face 54 at the dew pointtemperature. In an example the film 4 is maintained at a temperaturewhich has a predetermined offset from the dew point. The offset, ifused, is chosen to prevent the formation of water droplets on thesurface of the carbon nanotube film because water droplets may erodesurfactant from the film. The reference R_(D) may be chosen to providethe offset. The controller acts as the controller of a feedback loop inwhich the reference R_(D) (reference dew point resistance) is thereference value and the actual resistance R_(A) of the carbon nanotubefilm 4 is the controlled variable, R_(A), being controlled to equalR_(D) by varying the cooling of the film. The temperature T_(D) sensedby the temperature sensor 54 is the dew point or a temperature offset bya predetermined amount from the dew point temperature.

Variations in ambient conditions are tracked by variations in theresistance, R_(A) of the film 4 and controlling the temperature T of thecooled face to maintain the resistance of the film 4 at the referencedew point resistance R_(D) or at the predetermined offset from the dewpoint.

The reference value R _(D) may be established by cooling the film andobserving the surface of the film optically (using for example amicroscope) to determine when dew just forms on the surface andmeasuring the resistance of the film at that point. The measuredresistance is the reference value representing the dew point. If theoffset is used the value of R_(D) is adjusted accordingly. The surfaceof the film may be observed optically by a person using a microscope orit may be observed using a laser and detecting laser light scatteredfrom the surface as in a cold mirror dew point sensor.

A second way, which uses the processor 56, will now be described withreference to FIGS. 9 to 12.

FIG. 9 is a graph of an experimental result using SDS impregnated SWNTfilm. In the experiment, the SWNT film starts at room temperature and iscooled by the cooler. On cooling, the SWNT film's resistance (Res)initially increases very slowly, but near the dew point the resistanceincreases rapidly. When the cooling is stopped (by warming the sensor),the film resistance drops equally rapidly, before returning close to itsoriginal value. The resistance curve takes on a characteristic ‘peaked’profile when SWNT Resistance and Temperature are plotted against time.The line labelled ‘Dewpoint’, was obtained using a Testo 610 instrumentwhich derives the dew point temperature from its relative humiditymeasurement. The exact shape of the resistance curve depends on thecooling and heating rates obtaining during the test. Faster rates,produce curves with sharper peaks

FIG. 10 is a graph of a comparison of SDS impregnated SWNT film A andwashed film (i.e. SDS removed) B. For the normalised curves shown in thegraph, the increase in resistance as the sample is cooled (temperaturecurves not shown, for clarity) to the dew point is almost completelysuppressed when the film with the SDS surfactant removed, by washingwith deionized water, is tested (curve B).

FIG. 11 illustrates a way of determining the actual dew point. Thismethod uses the intersection of straight line fits to the slow and fastchanging parts of the SWNT resistance curve. The position P (time andtemperature) of intersection of the straight lines is assumed to be thedew point giving the dew point temperature. As shown in FIG. 12described below the assumed dew point is actually offset from the actualdew point. The processor 56 is programmed to record the variations ofresistance R and temperature T as the film is cooled and heated and tofit the straight lines to the resistance curve and to find theintersection of the straight lines.

The method of line fitting described with reference to FIGS. 9, 10 and11 to derive dew point temperatures and comparing them with readingsfrom a Testo 610 meter, recorded during the same cooling cycle, yieldsthe graph of FIG. 12. The relationship is linear, although the slope andoffset indicate that the curve fitting technique does not yield the truedew point temperature, but an offset value. Since the measurement isdependent on the shape of the curves and not the absolute value ofresistance, it is robust to erosion of the surfactant when condensationforms on the film surface, as discussed above.

The above embodiments are to be understood as illustrative examples ofthe invention. Further embodiments of the invention are envisaged. Forexample, referring to FIG. 13, instead directly measuring resistance ofthe carbon nanotube film 4, the film may be part of a resonant circuitand variations in amplitude of a resonant signal may be used as ameasure of water vapour sensed by the film 4. In one example the film 4forms at least one electrode 4 of a capacitor C in an RC or RLC resonantcircuit. The resistance of the film which provides at least part of theresistance R in the circuit (and not the capacitance of the capacitor C)varies with the sensed amount of water vapour.

It is to be understood that any feature described in relation to any oneembodiment may be used alone, or in combination with other featuresdescribed, and may also be used in combination with one or more featuresof any other of the embodiments, or any combination of any other of theembodiments. Furthermore, equivalents and modifications not describedabove may also be employed without departing from the scope of theinvention, which is defined in the accompanying claims.

1-12. (canceled)
 13. A method of making a water vapour sensorcomprising: depositing a liquid containing carbon nanotubes impregnatedwith surfactant on an inert substrate; drying the liquid on thesubstrate to form a film of carbon nanotubes impregnated with surfactanton the substrate; and connecting spaced apart zones of the film toelectrical conductors.
 14. A method according to claim 13, comprisingremoving surfactant from the zones.
 15. A method according to claim 13,wherein the surfactant is SDS (sodium dodecyl sulphate), SDBS (sodiumdodecyl benzene sulfonate), CTAB (Hexadecyl Trimethyl Ammonium Bromide),or polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether.
 16. Amethod according to claim 15, comprising impregnating the carbonnanotubes with surfactant.
 17. A method according to claim 16, whereinthe impregnating includes: mixing carbon nanotubes in a solution ofsurfactant and deionized water; and sonicating the mixture of carbonnanotubes and surfactant without removing the surfactant.
 18. A methodaccording to claim 17, wherein the mixing includes mixing single walledcarbon nanotubes in a solution of surfactant and deionized watercontaining a concentration of surfactant above a critical micelleconcentration.
 19. A method according to claim 18, wherein thedepositing includes spraying the mixture of carbon nanotubes andsurfactant on to a heated polyethylene terephthalate substrate.
 20. Ahumidity sensor comprising: carbon nanotubes impregnated with asurfactant; a measuring device operatively connected to the impregnatednanotubes to measure an electrical resistance of the impregnatednanotubes; and a processor operatively connected to the measuring deviceto determine a humidity based on the measured resistance.
 21. Thehumidity sensor of claim 20, wherein the impregnated nanotubes comprisea mixture of metallic and semiconductive carbon nanotubes impregnatedwith the surfactant.
 22. The humidity sensor of claim 21, wherein theimpregnated nanotubes comprise single walled carbon nanotubes,multiwalled carbon nanotubes, or a mixture of single and multiwalledcarbon nanotubes impregnated with the surfactant.
 22. The humiditysensor of claim 22, comprising a substrate supporting the impregnatednanotubes, the substrate being inert to the impregnated nanotubes. 23.The humidity sensor of claim 20, comprising a temperature sensoroperatively connected to the impregnated nanotubes to sense thetemperature of the impregnated nanotubes, and wherein the processor isoperatively connected to the temperature sensor to determine thehumidity based on the measured resistance and the sensed temperature.24. A dew point sensor, comprising: a cooler; a film of carbon nanotubesimpregnated with a surfactant operatively connected to the cooler; ameasuring device to measure an electrical resistance of the film ofcarbon nanotubes; a temperature sensor to sense a temperature of thefilm of carbon nanotubes; and a processor operatively connected to themeasuring device and the temperature sensor to determine a dew pointbases on the measured resistance and the sensed temperature.
 25. The dewpoint sensor of claim 24, wherein the cooler includes a cooled face andthe film of carbon nanotubes is disposed directly on the cooled face.26. The dew point sensor of claim 24, wherein the film of carbonnanotubes includes a mixture of metallic and semiconductive nanotubesimpregnated with the surfactant.
 27. The dew point sensor of claim 24,wherein the film of carbon nanotubes includes single walled nanotubes,multiwalled nanotubes, or a mixture of single and multiwalled nanotubesimpregnated with the surfactant.